ENHANCING CALCIUM RECOVERY BY INTRODUCTION OF

PURE CALCIUM CORED WIRES IN STEEL LADLES

Amit Kamble, David Lawrance, P.K.Sinha and S.B.Misra,

ABSTRACT

Development of continuous casting process (for billets, blooms, slabs, thin slabs
and thin strips) and newer products need stringent quality control during steel making to
ensure smoother casting operation as well as to allow casting at higher speeds.
Calcium treatment of steel in secondary refining, thus, has become necessary with
the increase in continuous casting ratio and nowadays is a well established method to
transform oxide and sulphide inclusions in steel to less harmful inclusions which can have
even beneficial effects to steel properties. Nozzle blockage problems in continuous casting
can be minimized by transformation of solid alumina inclusions in to liquid calcium
aluminates for aluminum killed steels. Also, introduction of calcium in low aluminium
(<0.005% Al) - Si killed steel results in reduced porosity in cast products by reducing the
dissolved oxygen content as it is a very strong deoxidizer as well
Introduction of calcium in liquid steel is difficult due to it’s low density, low melting
and boiling temperature and higher vapour pressure These problems have led to the
development of special addition technique like cored wire injection which comprises of a
continuous steel tube filled with calcium bearing materials
MINEX Metallurgical Company Limited is pioneer in production of cored wire
technology and manufactures whole range of cored wires including that of Ca based cored
wire for application in steel making. In normal practice recovery of Ca is in the range of
12-15% with cored wires of Ca-Fe, Ca-Fe-Al and Ca-Si. Introduction of newly developed
high performance pure calcium ( Ca>98%) cored wires have resulted in enhanced average
calcium recovery of more than 24% during treatment in ladle furnace. Theoretical aspects
of calcium treatment of steel along with salient results of plant scale trials of two variants
of pure calcium cored wire has been presented in this paper

Authors are with Minex Metallurgical Company Limited, Andheri(E), Mumbai 400 069
1.0 INTRODUCTION
There have been significant changes in
the specification of steel products. The service
requirement of these products have become
more and more severe over the last two
decades. Specifications are now more rigid to
meet the product requirements. Customer’s
demand has led to stringent steel quality with
respect to composition in a narrow range, high
degree of cleanliness, absence of segregation,
low gas content etc. The increasing demand for
high-quality steel products has led to the
continuous improvement of steelmaking
practices. There is a special interest in the
control of non-metallic inclusions due to their
harmful effect on the subsequent stages and
their great influence on the properties of the
final product. Through the control of the
amount, size and chemical composition of the
inclusions it is possible to obtain a final product
of good quality. There is an emerging trend of
reducing total non metallic residuals
(C,S,N,O,P,H) to very low levels. Secondary steel
making has played a vital role in meeting these
requirements
Treatment of liquid steel with calcium in
ladle refining process has become an important
means of deoxidation, desulphurization to very
low levels and to control the shape, size and
distribution of oxide and sulphide inclusions.
Benefits directly attributable to calcium
treatment include greater fluidity, smoother
continuous casting by reducing nozzle blockage
and improved cleanliness, machinability
ductility and impact strength in the final
product. Calcium injection into liquid steel helps
to liquefy the alumina. In this process, nozzle
clogging is also reduced; particularly in billet and
thin slab casting where the steel must pass
through narrow refractory spaces. In the
presence of sulphur, calcium also forms calcium
sulphide and MnS may precipitate on the CaS
nuclei (sulphide shape control).
Introduction of calcium in steel has
always been a challenge to steelmakers due to
low melting point (848oC), low boiling point
(1484 oC) and extremely low solubility. The
solubility of calcium in liquid iron (Fe) is reported
to be 300 ppm at 1600 oC and 1 atm of calcium
vapour pressure [1]. Under practical
steelmaking conditions, the concentration of
dissolved calcium depends upon; the time
available for the reactions to approach
equilibrium, stirring conditions, temperature
and composition of liquid steel at the time of
calcium injection, Vaporisation of calcium at
steelmaking temperatures and its low solubility
in iron are apparently the main causes of a low
calcium recovery.
1.1 Vapour Pressure of Calcium:
Vapour pressure of Calcium [2] at three
different temperature is given in Table below
and data for temperature range between 1550-
1650 deg C is presented in the Figure 1:
Temp, Deg C Vapour Pressure
(Atm)
1550 1.05
1575 1.4
1600 1.81
 Ca vapour pressure (Atm) at Various temp due to burning at top of ladle will be minimized
as the ferro-static pressure will be higher than
vapour pressure of calcium.
Ca vapour pressure, atm

2.2

1.8 1.2 Theoretical aspects of Ca treatment of

Steel
1.4
Alumina inclusions occur as deoxidation
1 products in the aluminium-based deoxidation of
1550 1575 1600 1625 1650 1675
Injection Tem p, deg c
steel Pure alumina has a melting point above
2000°C, i.e., these alumina inclusions are
Fig 1: Vapour pressure of calcium at different present in a solid state in liquid steel. The
injection temperatures addition of calcium to steel which contains such
inclusions changes the composition of these
Ferro- static pressure at different ladle heights inclusions from pure alumina to CaO-containing
is given in the Table below: calcium aluminates, as it can be observed from
the CaO-Al2O3 binary system, shown in Fig 2. [3].
Ht of liquid Ferro-static Ferro- static The melting point of the calcium aluminates will
steel in pressure, Pa pressure, decrease as the CaO content increases, until
ladle, Mtr Atm liquid oxide phases occur at about 22% of CaO,
1 76440 0.75
i.e., when the CaO.2Al2O3 compound is first
1.25 95550 0.94
exceeded at 1600ºC. The liquid phase content
1.4 107016 1.06
1.5 114660 1.13 continues to increase as CaO content rises
1.6 122304 1.21 further and is 100% at 35% of CaO. The
1.8 137592 1.36 minimum melting temperature for the liquid
2 152880 1.51 calcium aluminates is around 1400°C.
2.2 168168 1.66
2.4 183456 1.81
2.5 191100 1.89
2.8 214032 2.11
3 229320 2.26

From the above it can be inferred that the

vapour pressure of Calcium at treatment temp
of 1575 and 1600 deg C is 1.4 and 1.81 atm
respectively. If the calcium is released, before
the melting of sheath, at a depth of more than
2.0 meters for treatment temp of 1575 deg C
and at a depth of more than 2.4 meters for Fig 2 : CaO-Al2O3 Phase Diagram [3]
treatment at 1600 deg C then the loss of calcium
Thermodynamically, if sulfur or oxygen is aim is to obtain maximum content of C12A7
dissolved in the steel at moderate levels, or if liquid inclusions
Al2O3 inclusions are present in steel, calcium will
react with these. According to Larsen et al. [4] Ca Phase % CaO % Al2O3 Melting
will react with oxygen or sulfur until the Point , Deg C
contents of reactants are very low (< 2ppm). Pure Al2O3 0 100 2050
CA6 8 92 1833
Reaction of calcium when introduced in steel
can be represented by following set of CA2 22 78 1755
equations: CA 35 65 1590
Ca(l) = Ca (g) (i) C12A7 48 52 1395
Ca(g) = [Ca ] (ii)
C3A 62 38 1539
[Ca] +[O] = CaO (iii)
[Ca] +[S] = CaS (iv) CaO 100 0 2570
[Ca]+ (x+1/3)Al2O3=CaO*xAl2O3 + 2/3 [Al] (v)
(CaO)+2/3[Al] +[S]=(CaS) +1/3 (Al2O3) (vi) 1.4 Factors effecting Ca recovery

One of the critical questions is whether
or not calcium added to steel will react with
sulfur by reaction (iv) and form CaS or modify
Al2O3 to liquid Calcium aluminate by reaction (v).
The formation of calcium sulfide can occur if
calcium and sulfur contents are sufficiently high.
Since calcium has higher affinity for oxygen than
for sulfur, the addition of calcium initially results
in a more or less pronounced conversion of the
alumina into calcium aluminates until the
formation of calcium sulfides starts as the
addition of calcium continues. For steels with
low “S” content reaction (v) will take first
followed by reaction (vi).
1.3 Phases present during reaction of
calcium with alumina inclusions
Composition of various phases along
with their melting point is given below [5]. Main
To realize the benefits of cored wire
injection, it is imperative that the filling material
is released at such a depth in the ladle that the
resultant residence time is highest [6]. The wire
parameters which have been reported [6] to
influence the distance travelled are wire speed,
diameter, packing density of powders, casing
thickness etc. Also the steel temperature and
steel grade is reported to influence the depth of
release of the filler material. S.Basak et al [7]
have studied calcium recovery and efficacy of
calcium treatment using dimensional analysis
and electron microscopy. Industrial data during
Ca-Si cored wire injection in aluminium killed
steel have also been analysed. Calcium recovery
was found to increase with increased Si content,
while it decreased with increase in bath
temperature and calcium recovery was
maximum at a wire speed of 200 meter/minute.
2.0 CALCIUM CORED WIRES Product Composition (Weight %) Wire Density
for 13 mm dia
MANUFACTURED BY MINEX Ca Si Al Fe wire
(Grams/Meter)
Ca-Si 28-31 55-65 1.5 4.5 230 (±10)
Cored wire is manufactured at
cored Max Min
Kalmeshwar Industrial Zone in Nagpur, with wire
world-class manufacturing facility for Cored Ca-Fe 28-31 -- 1.5 68- 280(±10)
Wires functioning within Integrated cored Max 72
wire
Management Systems i.e. ISO-9001, EMS 14000 Ca-Fe-Al 38-42 -- 20 38- 200(±10)
and OHSAS 18001. Manufacturing facilities cored Min 40
include 5 cored wire drawing mills operating at wire

100 mtrs/min speed with annual production of

10,000 MT powder weight. One of the cored 3.0 EXPERIMENTAL
wire drawing mill is dedicated for production of
high performance calcium cored wire. The plant Many variants of pure calcium cored wires have
manufactures different types of cored wire for been developed by MINEX in last four years.
steel and foundry applications. The product Plant scale trial results of two such products are
range includes cored wires of Ca-Fe, Ca-Al-Fe, described in subsequent sections. Broad
Ca-Si, Ca, C, Fe-B, Fe-Ti, Fe-Mo,Fe-Nb, Fe-Si, specification of these are given as under:
Graphite, Lead, Fe-Si-Mg etc. The details of core
wire facility is given below: Pure Pure
Calcium Calcium
• Five Production Lines with all associated
cored wire cored wire
equipments. Variant “A” Variant “B”
• Wire diameters from 5mm to 21mm. Wire diameter, mm 9 9
• Automated powder fill control system for Density of wire, 50±2 67±2
+/- 5grms accuracy. grams/Mtr
Calcium purity, % >98 >98
• Maximum production speeds upto
100MPM.
It may be noted that both cored wires had
• Powder sizing and screening facilities.
different design features.
• Loading and unloading area for
approximate 30 Containers per day.
• Custom Bonded Ware House.

The composition and other details of various

calcium based cored wire conventionally used is
listed below. It may be noted that in cored wire
parlance density of cored wire means weight of
filler material in grams per meter of cored wire.
3.1 Plant Trials with Variant “A” Quantity of Calcium addition (Kg/t): 0.09-0.125
Speed of cored wire feeding (Meters/ Minute) :
Pure calcium cored wire treatment of 110-120
liquid steel was done at the end of refining in Temperature of treatment (deg C): 1580-1600
Ladle Furnace ie when the steel was fully Chemistry of steel treated with calcium is given
deoxidised, desulphurised to desired sulphur below:
levels and after the attainment of steel Grade C Mn S Si Al
chemistry. The aim was to attain calcium level in
the range of 15-25 PPM after treatment at LF. LCAK <0.1 0.2-0.35 <0.01 <0.05 0.03-0.05
The following were the injection parameters:

4.0 RESULTS AND DISCUSSIONS

Quantity of Calcium addition (Kg/t): 0.06-0.09
Speed of cored wire feeding (Meters/ Minute):
100-150
4.1 Trial results with Variant “A”
Temperature of treatment (deg C): 1580-1610
4.1.1 Calcium recovery
Chemistry of steel treated with calcium is given
below: Various data (Wire length fed in Mtr/t, calcium
addition in Kg/t, calcium content in PPM and
Grade C Mn S Si Al percent calcium recovery) of experimental heats
is shown in the following Table. Calcium content
LCAK <0.1 0.3- 0.004 - <0.05 0.03-
1.5 0.006 0.05 of steel after calcium treatment ranged between
14-25 PPM and percent calcium recovery varied
Al-Si 0.05- 1.0- 0.004 - 0.1- 0.03-
between 18-32%. Average Calcium recovery for
killed 0.15 1.3 0.006 0.25 0.05
these heats was 24.2%. It may be noted that
calcium recovery for steels treated with cored
3.2 Plant Trials with Variant “B”
wires of Ca-Si, Ca-Fe and Ca-Fe-Al was in the
range of 12-15% for Aluminium killed and Al-Si
Pure calcium cored wire treatment of
killed grades of steel.
liquid steel was done in another steel plant at
the end of refining in Ladle Furnace ie when the
steel was fully deoxidised, desulphurised to
desired sulphur levels and after the attainment
of steel chemistry. Here the aim was to attain
calcium level of more than 25 after treatment at
LF. The higher Ca level in this case is as per their
plant practice. Following were the injection
parameters:
 4.1.3 Effect of wire feeding speed of on
Heat Wire Ca Ca Calcium
Sl. length Addition content recovery calcium recovery
No. (Mtr/t) (Kg/t) (PPM) (%)
1 1.5 0.076 17 22.4 Highest average calcium recovery of
2 1.47 0.073 18 24.7 more than 25% has been attained at Wire
3 1.35 0.067 20 29.9 feeding speed of 120 meters/Minute [Fig.5].
4 1.72 0.080 23 27.0 Accordingly wire feeding speed has now been
5 1.72 0.085 15 17.6 optimised at this speed. It may be noted that
6 1.57 0.078 14 18.0 speed optimization is necessary for each cored
7 1.42 0.070 23 32.8 wire type and is plant specific.
8 1.72 0.085 14 16.5
9 1.31 0.065 14 21.6 26
10 1.56 0.077 22 28.5
25.5
11 1.81 0.09 25 27.9

Average Ca Recovery, %
Table : Experimental data of Pure Ca cored wire 25

of Variant “A” 24.5

24

4.1.2 Frequency distribution of calcium 23.5

recovery 23
Frequency distribution of calcium
22.5
recovery is shown in Fig.3. It may be noted that 80 100 120 140 160
heats having recovery of more than 25% was Speed of cored wire feeding
more than 40% whereas percent heats having
less than 20% calcium recovery was 25%. Fig 4: Effect of wire feeding speed on
average calcium recovery
45 41.7

40
4.2 Trial results with Variant “B”
35 33.3

30 4.2.1 Calcium recovery

Frequency, %

25
25

20 Various data (Wire length fed in Mtr/t, calcium

15 addition in Kg/t, calcium content in PPM and
10 percent calcium recovery) of experimental heats
5 is shown in the following Table. Calcium content
0 of steel after calcium treatment ranged between
<20 >20-25 >25
Ca Recovery,% 21-50 PPM and percent calcium recovery varied
Fig 3. Frequency distribution of calcium recovery between 22-49%. Average Calcium recovery for
these heats was 30.8%.
It may be noted that calcium recovery for steels may be noted that speed optimization is
treated with cored wires of Ca-Si, Ca-Fe and Ca- necessary for each cored wire type and is
Fe-Al was in the range of 12-15% for Aluminium plant specific.
killed and Al-Si killed grades of steel. Based on
our experience with variant ”A”, The speed of iv) Use of pure calcium cored wire will result
wire feeding was maintained at 110-120 in significant cost saving in Ca treatment
Mtrs/Min. due to enhanced recovery and also it will
facilitate reduction in inventory by
Heat Wire Ca Ca Calcium keeping stock of just one single type of
Sl. length Addition content recovery cored wire for all applications of Calcium
No. (Mtr/t) (Kg/t) (PPM) (%) treatment of liquid steel instead of
1 1.67 0.112 50 44.7 different cored wires of Ca-Fe, Ca-Fe-Al
2 1.35 0.091 45 49.5 and Ca-Si for various applications,
3 1.51 0.101 23 22.8
4 1.91 0.128 32 25.0 v) Our products at MINEX for calcium
5 1.37 0.092 30 32.7 treatment are constantly being upgraded
6 1.35 0.091 20 22.1 to achieve average calcium recovery of
7 1.86 0.124 33 26.5
more than 40% for all steel grades
8 1.33 0.089 21 23.7
Table : Experimental data of Pure Ca cored wire
6.0 REFERENCES
of Variant “B”
1. Wouter Tiekink et al, “Some aspects of the
5.0 CONCLUSIONS behaviour of calcium in low carbon low silicon
aluminium killed steel”, 13th IAS Steel Making
i) Average Calcium recovery for heats treated Seminar,2001, pp 340.
with pure calcium cored wire of variant ‘A”
was 24.2% (Range 18-32%) compared to 2. Ototani. T, Book on “Calcium Clean Steel”,
calcium recovery of 12-15% for steels Springer-Verlag Berlin, Heidelberg 1986,
treated with cored wires of Ca-Si, Ca-Fe and pp 6.
Ca-Fe-Al for Al and Al-Si killed steel. 3. Jose Carlos et al, “Modification of oxide inclusions
present in aluminium killed low carbon steel by
ii) Trials with variant “B” cored wire resulted in
addition of calcium”, Rem: Rev. esc. Minas, vol 57,
still higher average Calcium recovery of no.3, Ouro Preto, July/ Sept 2004
30.8% in the range of 22-49%. The higher
recovery in this case is attributed to 4. Larsen. K. et al. ISS Transactions, v.12, p.125-132,
improved design of this cored wire 1991.
compared to variant “A” 5. M. Lind, “Doctoral Thesis’, Helisinky University,
2006, pp 5
iii) Feeding speed for such cored wire has
been optimised at 120 meters/Minute It
6. Sarbendu Sanyal et al, “An improved model of
cored wire injection in steel melts”, ISIJ
International, Vol.44 (2004), No.7, pp 1157-1166

7. S. Basak et al, “Efficacy and recovery of calcium

during CaSi cored wire injection in steel melts”,
Iron Making and Steelmaking, 2010, vol 37, No.3,
pp 161-168

7.0 ACKNOWLEDGEMENTS

Authors gratefully acknowledge the

support provided by Mr. Atul Bhagat and Mr.
Shinu. K. of Minex Kalmeshwar plant for
designing, manufacture of cored wire and
participation in experimental work.